US4261858A - Catalyst for producing methacrylic acid - Google Patents
Catalyst for producing methacrylic acid Download PDFInfo
- Publication number
- US4261858A US4261858A US06/027,633 US2763379A US4261858A US 4261858 A US4261858 A US 4261858A US 2763379 A US2763379 A US 2763379A US 4261858 A US4261858 A US 4261858A
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- United States
- Prior art keywords
- catalyst
- methacrylic acid
- methacrolein
- antimony
- sub
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- This invention relates to a process and catalyst for the vapor-phase oxidation with molecular oxygen of methacrolein to methacrylic acid.
- unsaturated acids such as acrylic acid and methacrylic acid
- oxidation catalyst A variety of catalyst compositions have been proposed for this purpose. Many such compositions comprise the oxides of molybdenum and phosphorus in association with the oxides of various other elements, both metallic and non-metallic.
- British Pat. No. 1,430,337 and U.S. Pat. No. 4,000,088 propose the use of a catalyst composition in which the oxides of molybdenum and phosphorus are combined with the oxides of antimony, copper and rhenium and optionally with chromium.
- the catalyst does not contain calcium or rhenium.
- a catalyst containing rhenium as an optional ingredient is disclosed in U.S. Pat. No. 4,042,533.
- the catalyst lacks antimony, but requires the presence of tungsten and vanadium.
- Alkaline earth elements are included as optional ingredients.
- a catalyst of this type is not formulated merely by combining the many elements which have been disclosed in the prior art. Instead the catalyst performance must be determined experimentally at the expected operating conditions. Small changes in composition may be very important in achieving improved catalyst performance and particularly in optimizing the catalyst composition to suit a specific reaction and set of operating conditions. The point is well illustrated by the improvements in catalyst formulation to be described hereinafter.
- catalysts for oxidation of methacrolein to methacrylic acid have the characteristic property of remaining stable for a long period of time and then, without warning, of beginning of a rapid decline in activity. Consequently, an increase in the useful life of such catalysts has been sought, which has been achieved in the present invention by the addition of certain stabilizing ingredients.
- the catalyst composition may be regarded either as a mixture of oxides of the named elements or as oxygen-containing compounds of the elements or both.
- the catalyst composition used in the process of the invention also may be expressed by the following general formula:
- a to g indicate the atomic ratio of each component and, when a is 12, b is 0.05-3, c is 0.1-5, d is 0.1-0.7, e is 0.1-6, f is 0.005-0.5, and g has a value which is determined by the valence and proportions of the other elements in the catalyst.
- FIG. 1 graphically displays the change of reaction temperature over a period of operation to compare the useful life of oxidation catalysts.
- FIG. 2 shows the effect of varying the antimony content of catalysts according to the invention.
- the catalyst of the invention comprises oxides or oxygen-containing compounds of molybdenum, copper, phosphorus, antimony, calcium, and rhenium in predetermined atomic ratios, as expressed in the following general formula: Mo a Cu b P c Sb d Ca e Re f O g wherein a to g indicate the atomic ratio of each component and, when a is 12, b is 0.05-3, c is 0.1-5, d is 0.1-0.7, e is 0.1-6, f is 0.005-0.5, g is a value determined by the valence and proportions of the other elements in the catalyst. It has been found that the amount of antimony employed in the catalyst is particularly important.
- the addition of antimony in small amounts provides significantly improved conversion of methacrolein and with higher selectivity to methacrylic acid than when no antimony is used.
- further increase of antimony content causes a loss of both conversion and selectivity so that the amount of antimony should be limited to a value of about 0.7.
- the preferred value is about 0.3.
- Other elements which may be included in minor amounts in the catalyst formulation in order to promote catalyst activity or selectivity and without losing the advantages to be shown for the principal formula, are considered to be within the scope of the invention.
- the catalyst composition may be regarded either as a mixture of oxides of the named elements or as oxygen-containing compounds of the elements or both.
- the catalyst may contain either or both forms and both are intended to be included within the phrase "mixtures of oxides.”
- the catalyst composition is preferably used in unsupported form, e.g. in the form of pellets or other like compressed shapes of various sizes, although conventional supports could be employed instead.
- the composition may be formed in conventional manner using techniques well known to persons skilled in the art. For example, compounds of molybdenum, copper, phosphorus, antimony, calcium, and rhenium are dissolved in a small amount of water or other solvent, and the solutions are then combined and evaporated to dryness, e.g. in a rotary dryer.
- the several components can be introduced into solution in the form of various salts or other compounds of convenient types and no specific form for the catalyst precursors is necessary.
- ammonium salts, halides e.g.
- chlorides, nitrates or acid forms of the elements are, however, particularly suitable.
- aqueous solutions are employed and water-soluble forms of the elements are used.
- the solutions may have acids and/or bases added to them to facilitate dissolution of the catalyst precursors.
- acids such as hydrochloric or nitric acid, or bases such as ammonium hydroxide, can be used as desired.
- the resulting powder from the evaporation is then thoroughly dried and preferably screened to eliminate large particles which make it difficult to produce uniform compressed shapes, and as pellets. Typically, the powder is passed through a 20-mesh screen.
- the powder is then mixed with an organic binder which can be of any conventional type, such as polyvinyl alcohol, and the mixture is thoroughly dried and again screened, typically to provide a 20-80 mesh size.
- the dried mixture is then preferably combined with a lubricant, again of any conventional type, such as stearic acid or graphite, and compressed into the desired shape, e.g. pelletized, the compressed shapes typically having heights and diameters of 1/16 inch to 3/8 inch.
- the thus produced catalyst composition is activated at high temperature for a prolonged period in accordance with conventional practice in this art.
- the pellets are placed in an oven or kiln, or in a tube through which air is passed, at an elevated temperature (e.g.
- the temperature is raised at the rate of 20° C. per hour to a maximum of 420° C., preferably 320°-400° C., and this temperature is maintained for 16 hours.
- the catalysts described are generally useful for the production of unsaturated acids by oxidation with molecular oxygen of unsaturated aldehydes, although the reaction of methacrolein to form methacrylic acid is of particular interest.
- Other possible starting materials are the monoethylenically unsaturated aliphatic monoaldehydes of from 3 to 6 carbon atoms, such as acrolein, crotonaldehyde, 2-methyl-2-butenal, and the like, or mixtures thereof.
- the reaction in which the catalyst compositions of this invention are of particular utility and in which they provide high conversions and selectivities involves contacting the catalyst with methacrolein and oxygen in the vapor phase, preferably also in the presence of steam and diluents.
- the oxidation conditions employed are those generally associated with this reaction, although the molar ratio of oxygen to methacrolein should be kept at a high value near the flammable range in order to obtain the longest useful catalyst life.
- reaction is self-sustaining because of its exothermic nature.
- reactor types may be employed such as fluid or fixed bed types, but reactors having the catalyst disposed inside a multiplicity of heat exchanger tubes ae particularly useful and convenient.
- the gaseous feed to the reactor contains appropriate concentrations of methacrolein, oxygen and steam and usually an inert gas, such as nitrogen, is also present.
- the oxygen is usually added as such or as air, which may be enriched with oxygen.
- methacrolein can be present in concentrations of more than 5 up to about 20 volume percent of the total feed with a preferred range of more than 5 up to about 15 volume percent. In general at least 6 volume percent of the aldehyde is used in the feed.
- the corresponding ranges for oxygen are 3 to 15 volume percent, preferably 5 to 12 volume percent and for steam up to 50 volume percent, preferably 5 to 35 volume percent, the balance being the inert gas or gases.
- the temperature of the reaction should, for best results, be within the range of from about 270° to 450° C., preferably 280°-400° C., and the optimum temperature range is 290° to 325° C. Because the reaction is exothermic, means for conducting the heat away from the reactor are normally employed to avoid a temperature increase which favors the destruction of methacrolein by complete oxidation to carbon dioxide and water.
- the reactor temperature may be controlled by conventional methods such as by surrounding the catalyst-containing tubes with a molten salt bath.
- the reaction may be conducted at atmospheric, superatmospheric or subatmospheric pressure.
- pressures ranging from atmospheric up to about 8 kg/cm 2 absolute, preferably up to about 6.3 kg/cm 2 absolute, and most preferably up to about 4.5 kg/cm 2 absolute are employed.
- the unsaturated acid product may be recovered by a number of methods well known to those skilled in the art.
- the acid may be condensed, or scrubbed with water or other suitable solvents, followed by separation of the unsaturated acid product from the scrubbing liquid.
- the gases remaining after the acid-removal step are suitably recycled to the reaction, if desired, preferably after removal of CO 2 by conventional means, e.g., absorption in aqueous carbonate solution.
- the resulting powder is removed from the dryer and dried in an oven at 200° C. for 12 hours.
- the dried powder is screened through a 20-mesh screen, a 4% aqueous solution of polyvinyl alcohol is added in sufficient quantity to make a damp mixture and this mixture is dried at 75°-80° C. until the moisture content falls to 2-4 wt. %.
- the dried mixture is then screened to 20-80 mesh size particles, and about 2-6% of stearic acid powder is thoroughly mixed with it.
- the resulting mixture is then pelletized to form pellets of 3/16 inch height and diameter in which the catalyst components molybdenum, copper, phosphorus, antimony, and calcium are present in the atomic ratios of 12, 0.3, 1, 0.3 and 1.5, respectively.
- the pellets are then activated in an oven by heating them gradually at a rate of 20° C. per hour to 380° C. and maintaining them at this temperature for 16 hours.
- the activated pellets have a density of 0.97 gm/c
- a 150 cc quantity of the catalyst composition is placed in a reactor defined by a 1/2" ⁇ 90" stainless steel pipe, the reactor pipe being filled with 50 cc of inert filler (silicon carbide) below the catalyst bed and 100 cc of the inert filled above the catalyst bed in conventional manner to insure uniform temperature contact with the catalyst.
- Nitrogen-diluted mixtures containing methacrolein, oxygen and steam are fed to the reactor at a pressure of 1.74 kg/cm 2 (absolute) and at a space velocity of about 1200 hr -1 .
- space velocity is used in its conventional sense to mean liters of gas (at standard temperature and pressure) per liter of catalyst per hour.
- the feed composition is approximately, by volume, 6-7% methacrolein, 11-12% oxygen and 20% steam, the balance being nitrogen, determination being made on a wet basis.
- the reaction is run continuously and the exit gas is analyzed at intervals of several hours to give the overall effect of a series of different runs. Analyses are carried out by means of gas chromatography and by infrared spectrography using conventional techniques.
- Example 1 For comparison of many catalysts, all of which are capable of providing a satisfactory yield of methacrylic acid, but which differ in their useful life, an accelerated aging test is carried out on the catalyst of Example 1 and reported in FIG. 1.
- the catalyst is tested under severe conditions in order to obtain relatively quick determination of the catalyst performance by raising the operating temperature to the level needed to achieve at least about 80% conversion of methacrolein to methacrylic acid.
- the temperature most suitable for obtaining the best yield of methacrylic acid for a long period of useful catalyst life would be selected.
- the upper limit of catalyst temperature is reached when the target of 80% conversion can no longer be obtained.
- a catalyst corresponding to that of Example 1 is prepared by the same technique except that 38.1 grams of ammonium metal tungstate (NH 4 ) 6 H 2 W 2 O 40 . XH 2 O dissolved in 200 cc of water are included in the initial solution to provide tungsten in a catalyst having the following nominal composition:
- the catalyst also may contain boron at the ppm level since enough ammonium borate was included to provide 0.3 mols of boron.
- analysis of finished catalysts indicate that boron introduced into the solution in this manner is substantially lost, presumably by sumblimation during calcination, and if present, is below the level of detection by normal analytical methods, typically gravimetric and atomic absorption analysis.
- the catalyst is tested under the conditions of Example 2 and the results plotted in FIG. 1 where it may be compared with the results of Example 2.
- a catalyst corresponding to that of Example 1 is prepared by the same technique except that 5 grams of Re 2 O 7 dissolved in 100 cc of water are included in the initial solution to provide rhenium in a catalyst having the following nominal composition:
- Example 2 The catalyst is tested under the conditions of Example 2 and the results plotted in FIG. 1, where it may be compared to the results of Examples 2 and 3.
- Example 4 In order to demonstrate the importance of antimony in the catalyst of the invention, several catalysts were prepared according to Example 4, but the antimony content was varied. The catalysts were tested under the conditions of Example 2 except that no attempt was made to reach 80% conversion of methacrolein, but instead a determination was made as to the lowest temperature at which a satisfactory conversion and selectivity could be obtained. The results are shown in the following table.
- the data from the table are plotted in FIG. 2 which makes clear the critical importance of the antimony content in catalysts of this formulation.
- the conversion and selectivity figures are multiplied to provide a percentage yield of methacrylic acid (MAA) from the methacrolein fed.
- MAA methacrylic acid
- the yield of methacrylic acid is of particular importance with regard to commercial use of such catalysts, since the by-products are of lesser value.
- the figure clearly indicates that addition of antimony raises the yield of methacrylic acid remarkably, but that the yield appears to be maximized between say 0.1 and 0.7 and that about 0.3 is a preferred value. Further, by extrapolation, it appears likely that beyond about 0.9, addition of antimony gives a yield worse than that obtained with no antimony at all.
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- Organic Chemistry (AREA)
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Abstract
Description
Mo.sub.a Cu.sub.b P.sub.c Sb.sub.d Ca.sub.e Re.sub.f O.sub.g.
Mo.sub.12 Cu.sub.0.3 P.sub.1 Sb.sub.0.3 Ca.sub.1.5 W.sub.0.5 O.sub.i
Mo.sub.12 Cu.sub.0.3 P.sub.1 Sb.sub.0.3 Ca.sub.1.5 Re.sub.0.07 O.sub.i
______________________________________ Reactor Methacrolein Selectivity % to Sb Content Temp. ° C. Conversion, % Methacrylic Acid ______________________________________ 0 307 57 33 0.3 292 68 74 0.5 285 61 72 0.7 292 52 63 ______________________________________
Claims (1)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/027,633 US4261858A (en) | 1979-04-06 | 1979-04-06 | Catalyst for producing methacrylic acid |
NL7909142A NL7909142A (en) | 1978-12-26 | 1979-12-19 | CATALYST AND METHOD FOR PREPARING METHACRYLIC ACID. |
IT51168/79A IT1164100B (en) | 1978-12-26 | 1979-12-21 | CATALYST AND PROCESS TO PRODUCE METHACRYLIC ACID |
BR7908476A BR7908476A (en) | 1978-12-26 | 1979-12-21 | CATALYTIC COMPOSITION, CATALYST, AND, PROCESS FOR THE PREPARATION OF META ACRYLIC ACID |
FR7931595A FR2445310A1 (en) | 1978-12-26 | 1979-12-24 | CATALYST AND PROCESS FOR PRODUCING METHACRYLIC ACID BY OXIDATION OF METHACROLEINE IN THE STEAM |
GB7944392A GB2040717B (en) | 1978-12-26 | 1979-12-24 | Catalyst and process for producing methacrylic acid |
AR27944279A AR224753A1 (en) | 1978-12-26 | 1979-12-26 | CATALYZING COMPOSITION AND PROCEDURE FOR PRODUCING METHACRYLIC ACID WITH THE SAME |
DE2952455A DE2952455C2 (en) | 1978-12-26 | 1979-12-27 | Oxidation catalyst and its use |
MX180602A MX154396A (en) | 1978-12-26 | 1980-01-02 | IMPROVED CATALYST COMPOSITION FOR OBTAINING METHACRYLIC ACID |
GB08307119A GB2121309B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
GB08307118A GB2116063B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/027,633 US4261858A (en) | 1979-04-06 | 1979-04-06 | Catalyst for producing methacrylic acid |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US05/973,495 Continuation-In-Part US4252683A (en) | 1978-12-26 | 1978-12-26 | Catalyst for producing methacrylic acid |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/081,406 Continuation-In-Part US4271040A (en) | 1978-12-26 | 1979-10-03 | Catalyst and process for producing methacrylic acid |
US06/248,924 Continuation-In-Part US4547588A (en) | 1979-10-03 | 1981-03-30 | Process for producing methacrylic acid |
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Publication Number | Publication Date |
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US4261858A true US4261858A (en) | 1981-04-14 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US06/027,633 Expired - Lifetime US4261858A (en) | 1978-12-26 | 1979-04-06 | Catalyst for producing methacrylic acid |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3226721A1 (en) * | 1981-07-17 | 1983-04-21 | The Halcon SD Group, Inc., 10016 New York, N.Y. | METHOD FOR PRODUCING METHACRYLIC ACID |
US5833798A (en) * | 1996-04-17 | 1998-11-10 | Dow Corning S. A. | Adhesion method employing organosiloxane compositions |
US20070021629A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US20070021296A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
US20070021630A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US7649112B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
US20110064627A1 (en) * | 2007-02-14 | 2011-03-17 | Saudi Basic Industries Corporation | A quench column apparatus for separating methacrolein from methacrylic acid in a gas phase product from the partial oxidation of isobutene |
US8722940B2 (en) | 2012-03-01 | 2014-05-13 | Saudi Basic Industries Corporation | High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
US8921257B2 (en) | 2011-12-02 | 2014-12-30 | Saudi Basic Industries Corporation | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000088A (en) * | 1974-06-03 | 1976-12-28 | Nippon Kayaku Co., Ltd. | Oxidation catalyst for the manufacture of methacrylic acid |
US4045478A (en) * | 1975-02-28 | 1977-08-30 | Ube Industries, Ltd. | Method for the preparation of methacrylic acid |
US4085065A (en) * | 1976-10-19 | 1978-04-18 | The Standard Oil Company (Ohio) | Process for the preparation of unsaturated acids from unsaturated aldehydes |
-
1979
- 1979-04-06 US US06/027,633 patent/US4261858A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000088A (en) * | 1974-06-03 | 1976-12-28 | Nippon Kayaku Co., Ltd. | Oxidation catalyst for the manufacture of methacrylic acid |
US4045478A (en) * | 1975-02-28 | 1977-08-30 | Ube Industries, Ltd. | Method for the preparation of methacrylic acid |
US4085065A (en) * | 1976-10-19 | 1978-04-18 | The Standard Oil Company (Ohio) | Process for the preparation of unsaturated acids from unsaturated aldehydes |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3226721A1 (en) * | 1981-07-17 | 1983-04-21 | The Halcon SD Group, Inc., 10016 New York, N.Y. | METHOD FOR PRODUCING METHACRYLIC ACID |
US5833798A (en) * | 1996-04-17 | 1998-11-10 | Dow Corning S. A. | Adhesion method employing organosiloxane compositions |
US20100240925A1 (en) * | 2005-07-25 | 2010-09-23 | Saudi Basic Industries Corporation | Methods for making unsaturated acids using catalysts for methacrolein oxidation |
US20100260647A1 (en) * | 2005-07-25 | 2010-10-14 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid |
US20070021630A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US7649111B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
US7649112B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
US7732367B2 (en) | 2005-07-25 | 2010-06-08 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US20070021629A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US20070021296A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
US7851397B2 (en) | 2005-07-25 | 2010-12-14 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US20100323882A1 (en) * | 2005-07-25 | 2010-12-23 | Saudi Basic Industries Corporation | Methods for preparing catalysts for methacrolein oxidation |
US8889088B2 (en) | 2005-07-25 | 2014-11-18 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid |
US7923404B2 (en) | 2005-07-25 | 2011-04-12 | Saudi Basic Industries Corporation | Methods for preparing catalysts for methacrolein oxidation |
US7999133B2 (en) | 2005-07-25 | 2011-08-16 | Sabic Basic Industries Corporation | Methods for making unsaturated acids using catalysts for methacrolein oxidation |
US20110064627A1 (en) * | 2007-02-14 | 2011-03-17 | Saudi Basic Industries Corporation | A quench column apparatus for separating methacrolein from methacrylic acid in a gas phase product from the partial oxidation of isobutene |
US8921257B2 (en) | 2011-12-02 | 2014-12-30 | Saudi Basic Industries Corporation | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
US8722940B2 (en) | 2012-03-01 | 2014-05-13 | Saudi Basic Industries Corporation | High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
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